MXPA99006466A - Stable solid block detergent composition - Google Patents

Abstract

The dimensionally stable alkaline solid block warewashing detergent uses an E-form binder forming a solid comprising a sodium carbonate source of alkalinity, a sequestrant, a surfactant package and other optional material. The solid block is dimensionally stable and highly effective in removing soil from the surfaces of dishware in the institutional and industrial environment. The E-form hydrate comprises an organic phosphonate and a hydrated carbonate.

Description

STABLE COMPOSITION OF SOLID BLOCK DETERGENT FIELD OF THE INVENTION The invention relates to substantially inorganic mild alkaline detergent materials, which can be manufactured in the form of a solid block and packaged for sale. In the manufacture of the solid detergent, a detergent mixture is extruded to form the solid. The solid detergent soluble or dispersible in water is usually uniformly dispensed without falling short or exceeding the detergent concentration, from a spray type dispenser, which creates an aqueous concentrate by atomizing water on the soluble solid product. The aqueous concentrate is directed to a place of use, such as a dishwashing machine.

BACKGROUND OF THE INVENTION The use of solid block detergents in industrial and institutional cleaning operations was initiated in the technology claimed in the US reissue patents of Fernholz et al. Nos. 32,762 and 32,818. Additionally, the pelleted materials are shown in Gladfelter et al. , U.S. Patent Nos. 5,078,301, 5,198,198 and 5,234,615. The extruded materials are described in Gladfelter et al. , U.S. Patent No. 5,316,688. The solid block format is a safe, convenient and efficient product format. In the pioneering technology, attention was focused substantially on how to empty and solidify highly alkaline material, based on a substantial proportion of sodium hydroxide. The initial solid block products (and predecessor powder products) used a substantial proportion of a solidifying agent, sodium hydroxide hydrate, to solidify the cast material in a freezing process using the low melting point of sodium hydroxide monohydrate. (approximately 50 ° C-65 ° C). The active components of the detergent were mixed with the molten sodium hydroxide and cooled to solidify. The resulting solid was a solid sodium hydroxide matrix hydrated with the detergent ingredients dissolved or suspended in the hydrated matrix. In this solid casting of the prior art and other hydrated solids of the prior art, the hydrated chemicals were reacted with water and the hydration reaction is run to the substantial termination. Sodium hydroxide also provided substantial cleaning in the dishwasher system and other places of use that require complete and rapid dirt removal. In these ancient products, sodium hydroxide was an ideal candidate because the highly alkaline nature of the caustic material provided excellent cleaning. Another process of solid pouring sodium hydroxide and sodium carbonate using substantially hydrated sodium materials was described in Heile et al. , US Patent Nos. 4,595,520 and 4,680, 1 34. Similarly, the pioneering technology in relation to the use of solid pelleted alkaline detergent compositions in the form of a water-soluble bag assembly and an extruded alkaline solid material A water soluble film was also initiated by Ecolab I nc. These products within the water soluble bag can be inserted directly into a spray dispenser, where the water dissolves the bag and contacts the soluble or extruded solid peel, dissolves the effective ingredients of the detergent, creates an effective washing solution, which is directed to a place of use. In recent years, attention has been directed to producing a highly effective detergent material from less caustic materials, such as commercial soda, also known as sodium carbonate, due to the advantages of manufacturing, processing, etc. Sodium carbonate is a soft base, and is substantially less strong (it has a smaller Kb) than sodium hydroxide. In addition, on an equivalent molar basis, the pH of the sodium carbonate solution is a smaller unit than an equivalent solution of sodium hydroxide (an order of magnitude reduction in alkalinity strength). Sodium carbonate formulations were not given serious consideration in the industry for use in heavy duty cleaning operations due to this difference in alkalinity. The industry believed that the carbonate could not clean properly under the demanding conditions of time, type and load of dirt and temperature found in the institutional and industrial cleaning market. A few formulations based on sodium carbonate and solid have been manufactured in areas where cleaning efficiency is not vital. In addition to solid detergents made of substantially hydrated sodium carbonate, the carbonate content was at least about seven moles of water of hydration per mole of carbonate, and they were not dimensionally stable. The substantially hydrated block detergent tended to swell and break over aging. This swelling and cracking was attributed to changes in the hydration states of sodium carbonate within the block. Finally, the processing of molten hydrate can cause problems of stability in the manufacture of materials. Certain materials, at high melting temperatures in the presence of water, can decompose or revert to be less active or inactive materials. EP 0 363 852 discloses a particulate composition comprising sodium carbonate, sodium percarbonate and a stabilizer. This composition is described as a carrier of commercial soda peroxygen. WO 92/0261 1 is directed to the manufacturer of solid detergent compositions, cast, without swelling. This reference generally describes cleaning compositions containing hydratable chemicals, which are capable of forming various hydrated forms with significantly different densities. Accordingly, a substantial need has arisen for solid, mechanically stable carbonate detergent products, having an equivalent cleaning performance when compared to detergents based on caustic substance. In addition, a substantial need has arisen for successful non-melted processes to manufacture detergents based on sodium carbonate which form a solid with minimal amounts of water of hydration associated with the sodium base. These products and processes must combine ingredients and successfully produce a stable solid product that can be packaged, stored, distributed and used in a variety of use locations.

BRIEF DISCUSSION OF THE INVENTION The invention involves a solid block detergent based on a combination of a carbonate hydrate and a non-hydrated carbonate species solidified by a novel hydrated species which we call the form-form hydrate composition. The solid may contain other cleaning ingredients and a controlled amount of water. The solid carbonate based detergent is solidified by the form E hydrate, which acts as a binder material or binder dispersed through the solid. The binder of Form E comprises, to a minimum, an organic phosphonate and water, and may also have associated carbonate. The solid block detergent uses a substantial proportion, sufficient to obtain cleaning properties, of hydrated carbonate and non-hydrated carbonate formed in solid in a novel structure comprising a novel binder material of form E in a novel manufacturing process. The integrity of the detergent solid, comprising anhydrous carbonate and other cleaning compositions, is maintained by the presence of the binder component of form E comprising an organic phosphonate, substantially all the water added to the detergent system and an associated fraction of the carbonate. This hydrate-binding component of form E is distributed along the solid and joins the hydrated carbonate and the non-hydrated carbonate and other detergent components in a stable solid block detergent. The alkali metal carbonate is used in a formulation that additionally includes an effective amount of a hardness sequestering agent that sequesters hardness ions, such as calcium, magnesium and manganese, but also provides suspending and dirt removal properties. The formulations may also contain a surfactant system which, in combination with sodium carbonate and other components, effectively removes dirt at normal temperatures and usage concentrations. The block detergent may also contain other common additives, such as, surfactants, formers, thickeners, soil anti-redeposition agents, enzymes, chlorine sources, reductive bleaches or oxidants, defoamers, rinse aids, dyes, perfumes, etc. Such block detergent materials are substantially free of a component that can compete with the alkali metal carbonate for water of hydration and interfere with solidification. The most common interference material comprises a second source of alkalinity. The detergent contains less than one amount of solidification interference from the second alkaline source, and contains less than 5% by weight, preferably less than 4% by weight, of common alkalinity sources including either sodium hydroxide or a sodium silicate. alkaline sodium, wherein the Na20: SiO2 ratio is greater than or equal to about 1. Although a small proportion of sodium hydroxide may be present in the formulation to assist in performance, the presence of a substantial amount of sodium hydroxide may interfere with solidification. The sodium hydroxide preferentially binds water in these formulations and in effect prevents the water from participating in the hydrate binding agent of Form E and in the solidification of the carbonate. On a mole basis per mole, the solid detergent material contains more than 5 moles of sodium carbonate for each total mole of both sodium hydroxide and sodium silicate. We have found that a highly effective detergent material can be made with little water (i.e., less than 15.5% by weight, more specifically less than 10% by weight water) based on the block. The solid detergent compositions of Fernholz et al. they required, depending on the composition, a minimum of about 12-1 5% by weight of water of hydration for successful processing. The Fernholz solidification process requires water to allow the materials to flow as fluid or to flow as fusion enough when they are processed or heated, so that they can be emptied into a mold, such as a plastic bottle or capsule for solidification. At lower amounts of water, the material would be more viscous to flow substantially for the manufacture of effective product. However, carbonate-based materials can be made in low water extrusion methods. We have found that as the materials are extruded, the water of hydration tends to associate with the phosphonate component and, depending on the conditions, a fraction of the anhydrous sodium carbonate is used in the manufacture of the materials. If the added water is associated with other materials, such as sodium hydroxide or sodium silicates, insufficient solidification occurs leaving a product that resembles a slurry, slurry or slurry as wet concrete. We have found that the total amount of water present in the solid block detergents of the invention is less than about 11 to 12% by weight based on the total chemical composition (not including the weight of the container). The solid detergent comprises less than about 1.3, more preferably less than 0.9 to 1.3 moles of water for each mole of carbonate, most preferably about 1.25 moles of water per mole of carbonate. With this in mind for the purpose of this patent application, the water of hydration declared in these claims relates mainly to water added to the composition which is mainly hydrated and associated with the binder, comprising a fraction of sodium carbonate, Phosphonate and hydration water. A chemical with water of hydration that is added to the process or products of this invention, where hydration remains associated with that chemical (does not dissociate from the chemical or associate with another), is not considered in this description as water added to hydration. The solid, dimensionally stable solid detergents will comprise about 5 to 20% by weight, preferably 1 to 15% by weight, of anhydrous carbonate. The carbonate balance comprises carbonate monohydrate. There is no carbonate present of the formula Na2CO3, XH20, where X is between 2 and 12. In addition, a small amount of sodium carbonate monohydrate can be used in the manufacture of the detergent, however, such water of hydration is used in this calculation . For the purpose of this application, the term "solid block" includes extruded pelleted materials, having a weight of 50 grams to 250 grams, an extruded solid with a weight of about 100 grams or more, or a solid block detergent having a mass between approximately 1 and 1 kilograms.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a ternary phase diagram showing proportions of solid carbonate, water and aminotp sequestrant (methylene phosphonate) that allows the manufacture of the solid block detergent, containing the hydrated carbonate of hydrate of form E and carbonate hydrate with decomposition beginning temperatures shown in the shaded portions. Figures 2 to 10 are data differential scanning calorimeter (DSC) traces that refer to a sodium carbonate monohydrate; a solid composition of a sodium carbonate and an organophosphonate and a solid detergent comprising an anhydrous sodium carbonate mass bound in a block, the data of which demonstrates the production of a novel binder of Form E, comprising a hydrated carbonate composition of sodium and an organophosphonate. These Figures demonstrate the novel state of hydration and the structure of form E of the invention. Figure 11 is an isometric drawing of the wrapped solid detergent.

Figure 12 is a graphical representation of improved dispensing characteristics of the solid detergent containing the E-form, when compared to a caustic solid.

DETAILED DESCRIPTION OF THE INVENTION The solid block detergents of the invention comprise an alkalinity source, a sequestrant and an E-form hydrate binding agent.

Active ingredients The present method is suitable for preparing a variety of solid cleaning compositions, such as, for example, extruded peel detergent compositions, extruded block, etc. The cleaning compositions of the invention comprise conventional alkaline carbonate cleaning agent and other active ingredients that will vary according to the type of composition being manufactured. The essential ingredients are as follows: Solid matrix composition As this material solidifies, a simple E-form hydrate binder composition is formed. This hydrate binder is not a simple hydrate of the carbonate component. We believe that the solid detergent comprises a higher proportion of carbonate monohydrate, a portion of alkali metal carbonate not hydrated (substantially anhydrous) and the binder composition of form E comprising a fraction of the carbonate material, an amount of the organophosphonate and water of hydration. The alkaline detergent composition can include an amount of an alkalinity source that does not interfere with solidification and smaller but effective amounts of other ingredients, such as surfactant (s), a chelating agent / sequestrant including a phosphonate, polyphosphate, an agent bleach, such as encapsulated bleach, sodium hypochlorite or hydrogen peroxide, an enzyme, such as a lipase, a protease or an amylase, and the like.

Alkaline Sources The cleaning composition produced according to the invention may include minor but effective amounts of one or more alkaline sources to intensify the cleaning of a substrate and improve the performance of the removal of dirt from the composition. The alkaline matrix is bound in a solid due to the presence of the binder hydrate composition including its water of hydration. The composition comprises about 10-80% by weight, preferably about 1-5% by weight, of an alkali metal carbonate source, most preferably 20-60% by weight. The total alkalinity source may comprise about 5% by weight or less of an alkali metal hydroxide or silicate. A metal carbonate, such as carbonate, bicarbonate, sodium or potassium sesquicarbonate, mixtures thereof and the like may be used. Suitable alkali metal hydroxides include, for example, sodium or potassium hydroxide. An alkali metal hydroxide can be added to the composition in the form of solid beads, dissolved in an aqueous solution, or a combination thereof. The alkali metal hydroxides are commercially available as a solid in the form of pellets or pellets converted to pellets having a mixture of particle sizes or as an aqueous solution, such as, for example, as a 50% by weight and one to 73% solution. % in weigh. Examples of useful alkaline sources include a metal silicate, such as sodium or potassium silicate (with a ratio of M20: SiO2 from 1: 2.4 to 5: 1, M representing an alkali metal) or metasilicate; a metal borate, such as sodium or potassium borate, and the like; ethanolamines and amines; and other alkaline sources.

Cleaning agents The composition comprises at least one cleaning agent, which is preferably a surfactant or surfactant system. A variety of surfactants can be used in a cleaning composition, including anionic, nonionic, cationic and zwitterionic surfactants, which are commercially available from a number of sources. Anionic and nonionic agents are preferred. For a discussion of surfactants see Kirk-Othmer, Encvclopedia of Chemical Technology, Third Edition, volume 8, pages 900-912. The cleaning composition comprises a cleaning agent in an amount effective to provide a desired level of cleaning, preferably about 0-20% by weight, more preferably about 1.5-15% by weight. Anionic surfactants useful in the present cleaning compositions include, for example, carboxylates, such as, alkylcarboxylates (carboxylic acid salts) and polyalkoxycarboxylates, ethoxylated alcohol carboxylates, ethoxylated nonylphenol carboxylates, and the like; sulfonates, such as alkylsulfonates, alkylbenzenesulfonates, alkylarylsulfonates, fatty acid esters sulfonates, and the like; sulfates, such as sulfated alcohols, ethoxylated sulfated alcohol, sulphated alkylphenols, alkyl sulfates, sulfosuccinates, alkyl ether sulphates, and the like; and phosphate esters, such as alkyl phosphate esters, and the like. Preferred anionics are sodium alkylarylsulfonate, alpha-olefinsulfonate, and fatty alcohol sulphates. Nonionic surfactants useful in cleaning compositions include those having a polyalkylene oxide polymer as a portion of the surfactant molecule. Such nonionic surfactants include, for example, polyethylene glycol ethers capped with chlorine, benzyl, methyl, ethyl, propyl, butyl and other similar fatty alcohol alkyls; nonionic surfactants free of polyalkylene oxide, such as alkyl polyglycosides; esters of sucrose and sorbitan and their ethoxylates; ethylene diamine alkoxylated; alcohol alkoxylates, such as ethoxylated alcohol propoxylates, alcohol propoxylates, ethoxylated propoxylate propoxylates of alcohol, ethoxylated alcohol butoxylate, and the like, ethoxylated nonyl phenol, polyoxyethylene glycol ethers and the like; carboxylic acid esters, such as glycerol esters, polyoxyethylene esters, glycol esters and fatty acid ethoxylates, and the like; carboxylic amides, such as diethanolamine condensates, monoalkanolamine condensates, polyoxyethylene fatty acid amides, and the like; polyalkylene oxide block copolymers, including a block copolymer of ethylene oxide / propylene oxide, such as those commercially available under the tradename PLURON ICMR (BASF-Wyandotte), and the like; and other similar nonionic compounds. Silicone surfactants such as ABI L® B8852 can also be used. Cationic surfactants useful for inclusion in a cleaning composition for sanitizing or softening fabric, include amines, such as primary, secondary and tertiary monoamines with alkenyl or C18 alkyl chains, ethoxylated alkylamines, ethylenediamine alkoxylates, imidazoles, such as - (2-hydroxyethyl) -2-imidazoline, a 2-alkyl-1- (2-hydroxyethyl) -2-imidazoline, and the like; and quaternary ammonium salts, such as, for example, alkyl quaternary ammonium chloride surfactants, such as n-C 1 -C 8 alkyldimethylbenzylammonium chloride, n-tetradecyldimethylbenzylammonium chloride monohydrate, a substituted quaternary ammonium chloride naphthylene, such as dimethyl-1-naphthylmethylammonium chloride, and the like; and other similar cationic surfactants.

Other additives Solid cleaning compositions made in accordance with the invention may include conventional additives, such as, a chelating / sequestering agent., bleaching agent, alkaline source, secondary hardening agent or solubility modifier, detergent filler, defoamer, anti-redeposition agent, threshold agent or system, aesthetic enhancing agent (i.e., dye, perfume), and the like. The auxiliaries and other additive ingredients will vary according to the type of composition being manufactured. The composition includes a chelating / sequestering agent, such as, an aminocarboxylic acid, a condensed phosphate, a phosphonate, a polyacrylate and the like. In general, a chelating agent is a molecule capable of coordinating (i.e., binding) the metal ions commonly found in natural water to prevent metal ions from interfering with the action of the other detersive ingredients of a cleaning composition. The chelating / sequestering agent can also function as a threshold agent when it is included in an effective amount. A cleaning composition includes about 0.1 -70% by weight, preferably about 5-60% by weight, of a chelating / sequestering agent. Useful aminocarboxylic acids include, for example, N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), and the like. Examples of condensed phosphates useful in the present composition include sodium and potassium orthophosphate, potassium and sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate and the like. A condensed phosphate may also assist, to a limited extent, in the solidification of the composition by fixing the free water present in the composition as water of hydration. The composition may include a phosphonate, such as, 1-hydroxyethane-1,1-diphosphonic acid CH 3 C (OH) [PO (OH) 2] 2; aminotri (methylene phosphonic) N [CH2PO (OH) 2] 3; aminotri (methylene phosphonate), sodium salt ONa POCH2N [CH2PO (ONa) 2] 2; I OH 2-hydroxyethyliminobis (methylenephosphon) acid HOCH2CH2N [CH2PO (OH2) 2]; diethylenetriaminepenta (methylenephosphonic acid) (HO) 2POCH2N [CH2CH2N [CH2PO (OH) 2] 2]; diethylene tetrapentane (methylene phosphonate), sodium salt (x = 7); hexamethylenediamno (tetramethylenephosphonate), potassium salt C10H (28-x) N2KxO12P4 (x = 6); bis (hexamethylene) triam ino (pentamethylene phosphonic) (H02) POCH2N [(CH2) 6N [CH2PO (OH) 2] 2] acid; and phosphorous acid H3P03. A preferred phosphonate combination is ATMP and DTPMP. A neutralized or alkaline phosphonate, or a combination of the phosphonate with an alkaline source is preferred before being added to the mixture, so that there is little or no heat or gas generated by a neutralization reaction, when the phosphonate is added. Polymeric polycarboxylates suitable for use as cleaning agents have pendant carboxylate groups (-C02") and include, for example, polyacrylic acid, maleic / olefin copolymer, acrylic / maleic copolymer, polymethacrylic acid, copolymers of acrylic acid-methacrylic acid, polyacrylamide hydrolyzed, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, and the like For further discussion of chelating / sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition , volume 5, pages 339-366 and volume 23, pages 31 9-320, the description of which is incorporated herein by reference. Bleaching agents for use in cleaning compositions for lightening or bleaching a substrate, include bleaching compounds capable of to release a speci e of active halogen, such as Cl2, Br2, -OCI "and / or -OBr", under conditions normally encountered during the cleaning process. Bleaching agents suitable for use in the present cleaning compositions include, for example, chlorine-containing compounds, such as, chlorine, a hypochlorite, chloramine. Preferred halogen-releasing compounds include the alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, the alkali metal hypochlorites, monochloramine and dichloramine, and the like. Encapsulated chlorine sources can also be used to enhance the stability of the chlorine source in the composition (see, for example, U.S. Patent Nos. 4,61 8,914 and 4,830,773, the disclosure of which is incorporated herein by reference in the present). A bleaching agent may also be a source of active oxygen or peroxygen, such as, hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrates, potassium permonosulfate, and sodium perborate mono- and tetrahydrate, with or without activators , such as, tetraacetylethylenediamine and the like. A cleaning composition may include a minor but effective amount of a bleaching agent, preferably about 0.1-1 0% > by weight, preferably about 1-6% > in weigh.

Detergent builders or fillers A cleaning composition may include a minor but effective amount of one or more of a detergent filler, which does not perform as a cleaning agent per se, but cooperates with the cleaning agent to intensify the cleaning capacity global composition Examples of fillers suitable for use in the present cleaning compositions include sodium sulfate, sodium chloride, starch, sugars, C 1 -C 10 alkylene glycols, such as propylene glycol, and the like. Preferably, a detergent filler is included in an amount of about 1-20% by weight, preferably about 3-15% by weight.

Defoaming agents A lesser but effective amount of a defoaming agent may also be included to reduce foam stability in the present cleaning compositions. Preferably, the cleaning composition includes about 0.0001 -5% by weight of a defoaming agent, preferably about 0.01 -3% >; in weigh. Examples of defoaming agents suitable for use in the present compositions include silicone compounds, such as, silica dispersed in polydimethylsiloxane, fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters, alkyl phosphate esters, such as, monostearyl phosphate, and the like. A discussion of defoaming agents can be found, for example, in U.S. Patent No. 3, 048,548 to Martin et al. , U.S. Patent No. 3, 334, 147 to Brunelle et al. , and US Patent No. 3,442,242 to Rué et al. , the descriptions of which are incorporated herein by reference.

Anti-redeposition agents A cleaning composition may also include an anti-redeposition agent capable of facilitating sustained suspension of dirt in a cleaning solution and preventing the removed dirt from being redeposited on the substrate being cleaned. Examples of suitable anti-redeposition agents include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, styrene maleic anhydride copolymers, and cellulosic derivatives, such as hydroxyethylcellulose, hydroxypropylcellulose, and the like. A cleaning composition may include about 0.5-10% by weight, preferably about 1-5% by weight, of an anti-redeposition agent.

Dyes / flavors Various colorants, flavors including perfumes, and other aesthetic enhancing agents may also be included in the composition. Dyes may be included to alter the appearance of the composition, such as Direct Blue® 86 (Miles), Fastusol® Blue (Mobay Chemical Corp.), Acid Orange® 7 (American Cyanamid), Basic Violet® 1 0 (Sandoz), Acid Yellow® 23 (GAF), Acid Yellow® 17 (Sigma) Chemical), Sap Green® (Keyston Analine and Chemical), Metanil Yellow® (Keystone Analine and Chem ical), Acid Blue® 9 (Hilton Davis), Sandolan Blue / Acid Blue® 1 82 (Sandoz), Hisol Fast Red® (Capitol Color and Chemical); Fluorescein® (Capitol Color and Chemical), Acid Green® 25 (Ciba-Geigy), and the like. Fragrances or perfumes that may be included in the compositions include, for example, terpenoids, such as citronellol, aldehydes, such as amyl cinnamaldehyde, a jasmine such as CIS-jasmine or jasmal, vanillin, and the like.

Aqueous Medium The ingredients may optionally be processed in a minor but effective amount of an aqueous medium, such as water, to achieve a homogeneous mixture, to assist in solidification, to provide an effective level of viscosity to process the mixture, and to provide the composition processed with the desired amount of firmness and cohesion during discharge and over hardening. Typically, the mixture during processing comprises about 0.2-12% by weight of an aqueous medium, preferably about 0.5-1.0% by weight.

Processing of the composition The invention provides a method for processing a solid cleaning composition. According to the invention, a cleaning agent and other optional ingredients are mixed with an effective solidifying amount of ingredients in an aqueous medium. A minimum amount of heat can be applied from an external source to facilitate the processing of the mixture. A mixing system provides continuous mixing of the ingredients at high cut to form a substantially homogeneous liquid or semi-solid mixture, in which the ingredients are distributed through their dough. The mixing system includes means for mixing the ingredients to provide effective cutting to maintain the mixture at a flowable consistency, with a viscosity during processing of about 1,000-1,000,000 cP (1 -1,000 Paos), preferably approximately 50,000-200,000 cP (50 to 200 Paos). The mixing system is preferably a continuous flow mixer or more preferably, a single or double screw extruder apparatus, with a twin screw extruder being highly preferred. The mixture is normally processed at a temperature to maintain the physical and chemical stability of the ingredients, preferably at ambient temperatures of about 20-80 ° C, more preferably about 25-55 ° C. Although limited external heat may be applied to the mixture, the temperature reached by the mixture may rise during processing due to friction, variations in ambient conditions, and / or by an exothermic reaction between the ingredients. Optionally, the temperature of the mixture can be increased, for example, in the entrances or exits of the mixing system. An ingredient may be in the form of a liquid or a solid, such as a dry particulate, and may be added to the mixture separately or as part of a premix with another ingredient, such as, for example, the cleaning agent, the aqueous medium and additional ingredients, such as a second cleaning agent, an auxiliary detergent or other additive, a secondary curing agent, and the like. One or more premixes can be added to the mixture. The ingredients are mixed to form a substantially homogeneous consistency, wherein the ingredients are distributed substantially uniformly throughout the dough. The mixture is then discharged from the mixing system through a die or other configuration means. The profiled extrudate can then be divided into useful sizes with a controlled mass. Preferably, the extruded solid is packaged in the film. The temperature of the mixture, when discharged from the mixing system, is preferably low enough to allow the mixture to be emptied or extruded directly into a packing system without first cooling the mixture. The time between the extrusion and packing discharge can be adjusted to allow the hardening of the detergent block for better handling during further processing and packaging. The mixture at the point of discharge is at about 20-90 ° C, preferably about 25-55 ° C. The composition is then allowed to harden to a solid form that can vary from a low density, foam-like, malleable, caulking consistency, to a concrete-like block, molten, high-density solid. Optionally, heating and cooling devices can be mounted adjacent to the mixing apparatus to apply or remove heat, in order to obtain a desired temperature profile in the mixer. For example, an external heat source can be applied to one or more barrel sections of the mixer, such as the ingredient input section, the final outlet section and the like, to increase the flowability of the mix during processing. The temperature of the mixture during processing, including at the discharge port, is maintained at approximately 20-90 ° C. When the processing of the ingredients is complete, the mixture can be discharged from the mixer through a discharge die. The composition eventually hardens due to the chemical reaction of the ingredients forming the hydrate binder of Form E. The solidification process can last from a few minutes to about six hours, depending, for example, on the size of the extruded or emptied composition. , the ingredients of the composition, the temperature of the composition and other similar factors. Preferably, the cast or extruded composition "undertakes" or initiates hardening to a solid form within about 1 minute to about 3 hours, preferably about 1 minute to about 2 hours, preferably about 1 minute to about 20 minutes.

Packaging System The packaging or container receptacle may be rigid or flexible, and may be composed of any suitable material to contain the compositions produced according to the invention, such as, for example, glass, metal, plastic film or sheet, cardboard, composites of cardboard, paper, and the like. Advantageously, since the composition is processed at, or near, ambient temperatures, the temperature of the processed mixture is sufficiently low so that the mixture can be emptied or extruded directly into the container or other packaging system without structurally damaging the material. As a result, a wider variety of materials can be used to manufacture the container than those used for compositions that are processed and dispensed under molten conditions.

The preferred packaging used to contain the compositions is made from a flexible, easy-open film material.

Dispensing of the Processed Compositions The cleaning composition made according to the present invention is dispensed from an atomizer-type dispenser, such as that described in U.S. Patent Nos. 4,826,661, 4,690,305, 4,687, 1 21, 4,426,362 and in US Pat. U.S. Patent Nos. Re 32,763 and 32,88, the disclosures of which are incorporated herein by reference. Briefly, an atomizer-type dispenser operates by striking a water atomizer on an exposed surface of the solid composition to dissolve a portion of the composition, and then directing immediately the concentrated solution comprising the composition outside the dispenser to a storage tank or directly to a point of use. The preferred form of the product is shown in Figure 11. When used, the product is removed from the packaging film (for example), and inserted into the dispenser. The atomization of water can be done by a nozzle in a shape that conforms to the solid detergent form. The dispenser enclosure can also be tightly adjusted to the detergent form in a dispensing system that prevents the introduction and dispensing of an incorrect detergent.

DETAILED DISCUSSION OF THE DIAMETERS Figure 1 is a ternary phase diagram showing a solid block detergent composition comprising sodium carbonate, aminotri (methylene phosphonate) and water. In the region defined by ABCD, several areas show proportions of materials that develop a hydrate material that decomposes at certain hydrate decomposition initiation temperatures as shown. Regions 2 and 3 are characteristic of preferred solid detergent compositions containing the hydrate binder of Form E. Figure 2 is a DSC trace of a sample of ash and water mixed in the proportions of monohydrate in a laboratory prepared sample and it allows them to age over 24 hours at 37.8 ° C. This material has an onset of hydrate decomposition of about 1 10 ° C, which is characteristic or typical for sodium carbonate monohydrate. All DSC curves included with this chart were run on a Perkin Elmer DSC-7 Model. Figure 3 is a DSC curve for a mixture of sodium carbonate (ash), ATMP and water at a ratio of 50 to 3.35 to 1 1 .4, respectively. The sample is mixed again in the laboratory and allowed to age in an oven at 37.8 ° C for a period of 24 hours. The starting temperature of the resulting solid has changed to 122 ° C, which we believe is characteristic of the form-binding hydrate binding agent comprising ATMP, hydrated and non-hydrated ash and water. The change in the start temperature results from the association of phosphonate ash hydrate and water in the ligation agent of form E.

Figure 4 is a DSC curve of an extruded product. The material of the experiment had the following formula: The product was formulated as follows: 2% of the nonionic was premixed with the large granular sodium trioliphosphate (STPP), the premix of surfactant D and the aminotri (methylene phosphonate) (ATMP) in a first powder feeder. The purpose of this premix was to sustain a thin spray dried ATMP NSD together with the large granular STPP to avoid segregation during processing. The anhydrous sodium carbonate (ash) is fed with a second powder feeder and the remaining water and surfactant were pumped together by separate pumps to a Teledyne processor equipped with extrusion screw sections. The production rate for this experiment was 1 3.6 kg / minute) and a batch of 544 kg of product was produced. In the DSC curve in Fig. 4, the tip closely resembles the hydration tip of the E-shaped complex seen in Figure 3. The decomposition onset temperature shifts to 1 28 ° C unlike the ash monohydrate seen in Figure 2 at about 1 10 ° C. Figure 5 shows the difference between a sodium carbonate monohydrate composition and the sodium carbonate composition formed in a solid using the hydrate material of Form E in the invention. Figure 5 contains two DSC curves, a first curve comprising a line having an intermnt point, and a second curve comprising a solid line. The curve having an included point represents the solid detergent bound in a solid material using the form-form hydrate. The solid line represents a material formed by exposing the solid detergent composition of the invention containing the hydrate-binding agent of Form E to the humid atmosphere of the environment. The solid detergent of the invention is combined with the humidity of the ambient atmosphere and forms sodium carbonate monohydrate, which is represented by the appearance of a secondary peak at a characteristic monohydrate temperature to the left of the hydrate peak of form E principal. A third smaller peak is shown to the left of both the E-form hydrate and a monohydrate peak. This peak is attributed to the formation of a seven mole hydrate during the combination of the humidity of the ambient atmosphere with the anhydrous sodium carbonate in the solid block detergent of the invention. Figure 6 shows a comparison similar to that shown in Figures 2 and 3. Figure 6 shows two curves. The solid line represents a solid block detergent of the invention containing the form-E hydrate. The interrupted line exhibits the thermal characteristics of the ash hydrate alone. The difference in temperature peaks shows that the ash monohydrate formed under the conditions of the experiment is substantially different than the hydrate material of form E of the invention. Figures 7 to 10 compare a complex of amiotri ash (methylene phosphonate) formed in varying molar proportions with the cast solid detergent material of the invention. This series of DSC curves show that as the ratio of ash to ATMP approaches about 5 to 1, the curves more closely represent the hydrate material of Form E of the invention. Based on these differential tracking calorimetry traces, we believe that the E-form hydrate material has a molar ratio of ash to ATMP of about 5: 1, however, some proportion of the hydrate material of form E is formed at proportions that they vary from approximately 3: 1 to approximately 7: 1 ash: ATMP. Figure 11 is a drawing of a preferred embodiment of the packaged solid block detergent of the invention. The detergent has a unique compressed waist elliptical profile. This profile ensures that this block, with its particular profile, can be adjusted only to spray dispensers having a correspondingly configured location for the solid block detergent. We are oblivious to any solid block detergent that has this form in the market. The shape of the solid block ensures that no unsuitable substitute for this material is easily placed in the dispenser for use in a dishwashing machine. In Figure 1 1, the overall product 1 0 is shown having a solid block emptied 1 1 (revealed by the removal of the package 12). The package includes a label 13. The film wrap can be easily removed using a tear line or fracture line 14 or 14a incorporated in the wrapper. We have also conducted dispensing experiments with formula substantially similar to those in formulas 1 and 2. Surprisingly, we have found that in the conductivity-based dispensing operation the control over dispensing of detergents based on sodium carbonate can be significantly better than the control over detergents based on caustic substance. We have found under normal dispensing conditions, that detergents based on caustic substance can frequently exceed target levels to a greater degree than ash-based detergents. We have also found that in detergents based on sodium carbonate, after a first or second cycle, the amount of detergent dispensed in each cycle does not vary from a target concentration, for example, about 800-1200 ppm of active ingredient by more than about 2%. These data are shown in Fig. 12. In Fig. 12, the vertical axis is the concentration in ppm and the horizontal axis is time. Frequently, in the initial dispensing cycles using a new solid-block ash-based detergent, the first cycle or two cycles may have 50-80% of the desired amount of active ingredients. However, after these initial cycles, control over the amount of active ingredient (sodium carbonate) in the wash water is significantly improved.

In sharp contrast, using alkaline detergents based on caustic substance, even in initial cycles, the excess of the desired amount of caustic substance can often be as much as 1 00% or more. Even during normal usage cycles, the excess can vary between less than about 0.1% to about 20%). Although these exceeded values do not normally damage the cleaning ability, such excess may be, under certain circumstances, some uneconomical detergent material. The above specification provides a basis for understanding the broad requirements and limits of the invention. The following examples and test data provide an understanding of certain specific embodiments of the invention and contain a better embodiment. The invention will be further described by reference to the following detailed examples. These examples are not intended to limit the scope of the invention that has been set forth in the foregoing description. Variations within the concepts of the invention are apparent to those skilled in the art.

Example 1 The experiment was run to determine the level of water needed to extrude a sodium carbonate product. The product of this example is a pre-soaked product but it also applies to a dishwashing detergent product. A liquid premix was made using water, nonyl phenol ethoxylate with 9.5 moles of EO (N PE 9.5), a Direct Blue® 86 dye, a fragrance and a Silicone Antifoam® 544. These were mixed in a jacketed mixing vessel equipped with a marine propeller agitator. The temperature of this premix was held between 29-32 ° C to prevent gelation. The rest of the ingredients for this experiment were sodium tripolyphosphate, sodium carbonate and LAS 90% flakes, which were all fed by separate powder feeders. These materials were all fed to a 5.1 cm Teledyne pulp processor in the percentages shown in Table 2. The production rates for this experiment varied between 9,072 and 8.1 64 kg / min. The experiment was divided into five different sections, each section had a different liquid pre-mix feed rate, which reduced the amount of water in the formula. The percentage of these reductions can be seen in Table 2. The product was discharged from Teledyne through an elbow and a 3.8 cm diameter plumbing pipe. The proportions of water to ash for each of the experiments are included in Table 2. Also in this table are the results of the experiment, the highest levels of molar proportions of water to ash (approximately 1.8-1.5) produced cracking and severe swelling. Only when the water levels approached 1 .3 or less did no breakage or swelling of the blocks appear. The best results were observed at a 1.25 molar ratio of water to ash. This shows an example that a product based on extruded ash can be made, but the water level has to be maintained at lower levels in order to prevent breakage or severe swelling.

Example 2 The following example is an example of a dishwashing detergent produced in a 12.7 cm Teledyne pulp processor. The premix was made of Surfactant Premix 3 (which is 84% nonionic, a pluronic non-ionic type and 16%> of a mono- and di-alkyl phosphate ester (approximately C16) mixed with granular sodium tripolyphosphate Large and spray dried ATMP (aminotri (methylene phosphonic acid)) The spray dried ATMP was neutralized before being spray dried at a pH of 12-13.The purpose of this premix is to make a uniform material to be fed to the Teledyne without segregation occurs The formula for this experiment is as follows: TABLE 1 The dye, which is Direct Blue 86, was premixed in the mixing tank with soft water. The production speed for this experiment was 1 3.6 kg / minute and a 160 kg batch was made. The molar ratio of water to ash was 1 .3 for this experiment. The Teledyne process extruder was equipped with a round 14 cm elbow and straight sanitary pipe that fit into the discharge. The blocks were cut into blocks of approximately 1.4 kg. The Teledyne was run at approximately 300 rpm and the discharge pressure was approximately 1 38 kPa. The water temperature for this experiment was maintained at 1 5 ° C, the surfactant temperature was 26 ° C, and the average block discharge temperature was 46 ° C. The production ran well with blocks hardening 1 5-20 minutes after the Teledyne discharge, no cracking or swelling was noted for this experiment.

Example 3 Laboratory samples were made to determine the phase diagram of ATMP, sodium carbonate and water. The atomized spray-dried version of ATMP used in Example 2 is the same material used in this experiment. Lightweight anhydrous carbonate (FMC grade 100) and water were used for the other ingredients. These mixtures were allowed to react and equilibrate in an oven at 38 ° C overnight. The samples were then analyzed by DSC to determine the start of the hydration decomposition tip for each sample. The results of these experiments were a phase diagram, which can be seen in Figure 1. A displacement at the start of the hydrate decomposition temperature is observed as ATMP is added to the mixtures seen. The normal monohydrated ash tip is seen at very low levels of ATMP. But with increased amounts of ATMP, there is a region of higher proportions of a more stable form E hydrate binding agent, which we believe is a complex of ATMP, water and ash. We also believe that this is a composition which is responsible for much, of the improved hardness of the blocks with products containing ATMP. Blocks containing ATMP are less likely to break apart than blocks that do not contain ATMP. In addition, blocks containing ATMP may contain a higher water level than blocks that do not contain ATMP.

Example 4 For this experiment, we ran the same experiment as in the Example 3, except that Bayhibit AM (which is 2-phosphonobutane-1, 2,4-tricarboxylic acid) was replaced by the ATMP. The material used was neutralized at a pH of 12-1 3 and dried. Mixtures of this material, ash and water, were then prepared and allowed to equilibrate overnight in an oven at 38 ° C. The samples were then analyzed by DSC for the start of the hydration decomposition temperature. This system gave comparable results with a higher start of hydration decomposition. At this time, we believe that a solid based on extruded, improved ash can be obtained by adding a phosphonate to the formula.

We believe that the E-form complex, water, ash, phosphonates, is the main solidification method for these systems. This is a superior solidification system for the existing ash monohydrate, as it provides a much harder, stronger and less prone to cracking and swelling.

TABLE 2 EXAMPLES OF THE PATENT OF A PRE-REMOVED PRODUCT LIQUID PREMIZCLA OF THE FIRST LIQUID PORT Example 5 A detergent based on sodium carbonate (formula 1) was tested. a detergent based on NaOH (formula 2). The compositions of these two formulas are listed in Table 3.

TABLE 3 (I I) Test Procedures A lipstick, protein, film and stain removal test of 10 cycles was used to compare formulas 1 and 2 under different test conditions. In this test procedure, Libbey milk-coated and clean cups were washed in an institutional dishwashing machine (a Hobart C-44) together with a laboratory dirt and detergent formula test. The concentrations of each one remained constant throughout the 10-cycle test. Laboratory dirt is a 50/50 combination of hot spot dirt and stewed meat. Warm knit dirt is hydrophobic, greasy dirt made from 4 parts of Blue Bonnet® all-vegetable margarine and 1 part of Carnation® instant non-greasy milk powder. In this test, the milk-coated cups are used to test the dirt removal capacity of the detergent formula, while the initially clean cups are used to test the anti-redeposition ability of the detergent formula. At the end of the test, the glasses are classified by removal of lipstick, protein, film and spots. The rating scale is from 1 to 5, with 1 being the best and 5 the worst results. (lll) Test results In Example 1, formula 1 was compared to formula 2 in the 10-cycle lipstick, protein, film and stain removal test, under 1 00 ppm detergent, 500 ppm dirt food, and 5.5 grains of city water conditions (moderate hardness). The results of the test are listed in Table 4.

TABLE 4 These results show that under normal soil conditions and low water hardness, ash-based formula 1 performs as well as formula 2 based on caustic substance.

Example 6 In Example 6, formula 1 was compared to formula 2 in the 10-cycle lipstick, protein, film and stain removal test, under 1500 ppm detergent, 2000 ppm food dirt, and 5.5 grains of water conditions of city. The results of the test are listed in Table 5.

TABLE 5 These test results show that under hard conditions of dirt and low water hardness, higher concentrations of detergent can be used to obtain good spots, film and protein results, which are comparable with those obtained in Example 5.

Surprisingly, formula 1 exceeded the performance of formula 2 in the removal of lipstick by a large margin.

Example 7 In Example 7, formula 1 was compared to formula 2 in the 10-cycle lipstick, protein, film and stain removal test, under 1500 ppm detergent, 2000 ppm food dirt, and 18 grains of hard water conditions. The results of the test are listed in Table 6.

TABLE 6 These test results show that under conditions of high water hardness and hard dirt conditions, cleaning results generally suffer, even with higher concentrations of detergent. However, formula 1 exceeded formula 2, especially in the removal of lipstick.

Example 8 In order to evaluate the relative importance of the surfactant builder (LF-428, an extoxylate of 12 moles of linear alcohol of C? 2 .-? 4 capped with benzyl), and the strong chelating agent (aminotri (methylene) sodium phosphonate), in the ash-based detergent, four variations of formula 1 against each other were compared under 1000 ppm of detergent, 500 ppm of food dirt, and 5.5 grains of city water conditions. The results of the test are listed in Table 7.

TABLE 7 - Formula 1 A is Formula 1 without non-ionic - Formula 1 B is Formula 1 without non-ionic and sodium aminotri (methylene phosphonate) - Formula 1 C is Formula 1 without aminotri (methylene phosphonate) of sodium These test results show that, surprisingly, the chelating agents cooperate with alkalinity sources to remove dirt, such as in the removal of lipstick. The above specification, examples and data provide a recognized basis for understanding the technical advantages of the invention. However, since the invention may comprise a variety of embodiments, the invention resides in the claims appended hereto.

Claims (10)

1. REIVI NDICATIONS
2. 1 . A method for manufacturing a solid block detergent composition, characterized by containing at least 5 moles of carbonate per mole of alkalinity source, and further characterized by containing at least 12% by weight of water; said block comprising a detergent, said method comprises: (i) combining: (a) about 10 to 80% by weight of an anhydrous alkali metal carbonate; (b) about 1 to 30% by weight of an organic phosphonate hardness sequestering agent; and (c) about 0.01 to less than 1.3 mole of water per mole of carbonate to form a mixed mass, in which the ingredients are distributed substantially uniformly; and (ii) discharging the mixed mass through a die or other configuration means to form a solid comprising unhydrated alkali metal carbonate, and a binder comprising an alkali metal carbonate hydrate and organic phosphonate for solidification; wherein the solid block is substantially free of a second source of alkalinity. The method of claim 1, wherein the sodium carbonate comprises a monohydrate, and the solid block detergent composition comprises about 1.5 to 15% > by weight of a surfactant comprising an anionic surfactant, a nonionic surfactant and mixtures thereof. The method of claim 1, wherein the water is present in the solid block detergent composition in an amount of about 0.9 to 1 .
3. 3 moles of water per mole of carbonate.
4. 4. The method of claim 1, wherein the mixed mass is extruded to form a solid block detergent composition having a mass of 1 -1 0 kg.
5. 5. The method of claim 2, wherein the nonionic comprises a non-ionic detergent composition. The method of claim 1, wherein the mixed mass is formed into pellets, each pellet having a mass of about 50 to 250 grams. The method of claim 1, wherein the organic phosphonate sequestering agent is used in an amount of about 1 -30% by weight. The method of claim 1, wherein there is less than 1.25 moles of water per mole of sodium carbonate. The method of claim 2, wherein the solid block detergent composition additionally comprises a nonionic rinse agent. The method of claim 1, wherein the solid block detergent composition comprises about 3 to 20% by weight of the organic phosphonate and additionally comprises an inorganic fused phosphate.

   eleven . The method of claim 10, wherein the inorganic fused phosphate comprises a sodium tripolyphosphate sequestrant. The method of claim 1, wherein the solidified product is substantially free of Na2CO3"XH20, wherein X is a number ranging from about 2-12. The method of claim 1, wherein the solidified product is substantially free of sodium hydroxide. The method of claim 1, wherein the maximum temperature used in the forming step is less than the melting point of the mixed mass. 15. A solid block dishwashing detergent composition, comprising: (a) about 20 to 65% by weight Na2C03; and (b) about 1 to 30% by weight of an organic phosphonate hardness sequestering agent; wherein the block comprises unhydrated sodium carbonate and a binder comprising sodium carbonate hydrate and organic phosphonate, and wherein the block is substantially free of a second source of alkalinity. 16. The solid block dishwashing detergent composition of claim 1, characterized in that it comprises from about 0.9 to 1 .3 moles of water per mole of sodium carbonate. 17. The solid block dishwashing detergent composition of claim 1, wherein the hydrated sodium carbonate comprises a monohydrate and the solid block dishwashing detergent composition comprises about 1.5 to 15% by weight of a surfactant composition, comprising an anionic surfactant, a nonionic polymeric surfactant or mixtures of the same. 18. The solid block dishwashing detergent composition of claim 1, characterized by being extruded. 9. The solid block dishwashing detergent composition of claim 18, wherein the block has a mass greater than about 10 grams. 20. The solid block dishwashing detergent of claim 1, wherein the anionic surfactant comprises an anionic detergent composition. twenty-one . The solid block dishwashing detergent of claim 1, wherein the organic phosphonate sequestrant is present in an amount of about 0.5 to 20% by weight. 22. The solid block dishwashing detergent of claim 1, further comprising a nonionic detergent composition. 23. The solid block dishwashing detergent of claim 22, further comprising a non-ionic defoaming composition. 24. The solid block dishwashing detergent of claim 22 further comprises a non-ionic rinsing agent. 25. The solid block dishwashing detergent of claim 21, wherein the scavenger also comprises an inorganic fused phosphate. 26. The solid block dishwashing detergent of claim 25, wherein the sequestrant comprises about 3 to 20% by weight of the organic phosphonate, and additionally comprises a tripolyphosphate sequestrant. 27. The solid block dishwashing detergent of claim 1, wherein there is less than about 1.25 moles of water per mole of sodium carbonate. 28. The solid block dishwashing detergent of claim 15, which is substantially free of NaOH. 29. The solid block dishwashing detergent composition of claim 1, wherein the scavenger comprises 1 to 45% by weight of an inorganic tripolyphosphate and about 0.1 to 20% >; by weight of the organophosphonate sequestrant. 30. The solid block dishwashing detergent composition of claim 1, wherein the solid block comprises less than 1.25 moles of water per mole of sodium carbonate.